JP2023152988A - Ethylene-vinyl alcohol copolymer composition, pellet, multilayer structure, method for producing ethylene-vinyl alcohol copolymer composition, and method for producing multilayer structure - Google Patents
Ethylene-vinyl alcohol copolymer composition, pellet, multilayer structure, method for producing ethylene-vinyl alcohol copolymer composition, and method for producing multilayer structure Download PDFInfo
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- JP2023152988A JP2023152988A JP2023054956A JP2023054956A JP2023152988A JP 2023152988 A JP2023152988 A JP 2023152988A JP 2023054956 A JP2023054956 A JP 2023054956A JP 2023054956 A JP2023054956 A JP 2023054956A JP 2023152988 A JP2023152988 A JP 2023152988A
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- Prior art keywords
- evoh resin
- ethylene
- resin composition
- vinyl alcohol
- alcohol copolymer
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- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 50
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 48
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- 230000008859 change Effects 0.000 abstract description 12
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- GFQOFGWPGYRLAO-UHFFFAOYSA-N dodecanamide;ethene Chemical compound C=C.CCCCCCCCCCCC(N)=O.CCCCCCCCCCCC(N)=O GFQOFGWPGYRLAO-UHFFFAOYSA-N 0.000 description 1
- 235000015071 dressings Nutrition 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- WGTGQGJDNAGBCC-UHFFFAOYSA-N hex-5-ene-1,2-diol Chemical compound OCC(O)CCC=C WGTGQGJDNAGBCC-UHFFFAOYSA-N 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- MCCIMQKMMBVWHO-UHFFFAOYSA-N octadecanoic acid;titanium Chemical compound [Ti].CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O MCCIMQKMMBVWHO-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011129 pharmaceutical packaging material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- QWWIMOOFEDJKFN-UHFFFAOYSA-N titanium;dihydrate Chemical compound O.O.[Ti] QWWIMOOFEDJKFN-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、エチレン－ビニルアルコール系共重合体組成物、ペレット、多層構造体、エチレン－ビニルアルコール系共重合体組成物の製造方法及び、多層構造体の製造に関する。 The present invention relates to an ethylene-vinyl alcohol copolymer composition, pellets, a multilayer structure, a method for producing an ethylene-vinyl alcohol copolymer composition, and a multilayer structure.
エチレン－ビニルアルコール系共重合体（以下、「ＥＶＯＨ樹脂」と称することがある）は、透明性、酸素等のガスバリア性、保香性、耐溶剤性、耐油性、機械強度等に優れており、フィルム、シート、ボトル等に成形され、食品包装材料、医薬品包装材料、工業薬品包装材料、農薬包装材料等の各種包装材料として広く用いられている。 Ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as "EVOH resin") has excellent transparency, gas barrier properties against oxygen and other gases, fragrance retention, solvent resistance, oil resistance, mechanical strength, etc. It is formed into films, sheets, bottles, etc., and is widely used as various packaging materials such as food packaging materials, pharmaceutical packaging materials, industrial chemical packaging materials, and pesticide packaging materials.
しかし、ＥＶＯＨ樹脂は、分子内に比較的活性な水酸基を有するため、熱により劣化しやすい傾向があり、溶融成形時に着色の問題が起こりやすい。 However, since EVOH resin has a relatively active hydroxyl group in its molecule, it tends to be easily deteriorated by heat, and coloring problems are likely to occur during melt molding.
上記の課題に対し、例えば特許文献１では、ＥＶＯＨ樹脂に特定量の不飽和アルデヒドを含有させることにより、溶融成形時の酸化劣化が抑制され、着色が抑制できることが開示されている。 To address the above-mentioned problems, for example, Patent Document 1 discloses that by containing a specific amount of unsaturated aldehyde in EVOH resin, oxidative deterioration during melt molding can be suppressed and coloration can be suppressed.
近年、成型装置におけるフィードブロック・ダイ形状の多様化、最終製品における多層構造体の薄膜化や層数増加等の各種高機能化の要求に伴って、成形装置が高機能化する傾向がある。その反面、高機能化により複雑化した成形装置内で樹脂が熱劣化し、着色等が発生して製品の生産性が低下する傾向がある。
前記特許文献１では、溶融成形時の着色の抑制のために不飽和アルデヒドを用いているが、このようなアルデヒド化合物は、微量であっても悪臭の原因となることがある。特に高温に晒される溶融成形時において、アルデヒド化合物が揮発し、作業環境の悪化が懸念される。そのため、このような揮発する化合物を用いることなく、溶融成形工程時の着色が抑制された、すなわちロングラン性に優れるＥＶＯＨ樹脂組成物が求められている。
In recent years, there has been a tendency for molding equipment to become more sophisticated due to the diversification of feedblock and die shapes in molding equipment, and demands for various higher functionality such as thinner multilayer structures and increased number of layers in final products. On the other hand, resin tends to deteriorate due to heat in molding equipment that has become more complex due to higher functionality, causing coloring and the like, resulting in a decrease in product productivity.
In Patent Document 1, an unsaturated aldehyde is used to suppress coloring during melt molding, but even a trace amount of such an aldehyde compound may cause a bad odor. In particular, during melt molding when exposed to high temperatures, aldehyde compounds volatilize and there is concern that the working environment will deteriorate. Therefore, there is a need for an EVOH resin composition that suppresses coloring during the melt molding process without using such volatile compounds, that is, has excellent long-run properties.
本発明は、溶融成形時の熱劣化による着色変化が抑制されたＥＶＯＨ樹脂組成物の提供を目的とする。 An object of the present invention is to provide an EVOH resin composition in which color change due to thermal deterioration during melt molding is suppressed.
しかるに、本発明者等はかかる事情に鑑み、ＥＶＯＨ樹脂にチタン化合物を特定微量加えることにより、溶融成形時の熱劣化による着色変化が抑制されたＥＶＯＨ樹脂組成物が得られることを見出した。 However, in view of such circumstances, the present inventors have discovered that by adding a specific trace amount of a titanium compound to EVOH resin, an EVOH resin composition can be obtained in which color change due to thermal deterioration during melt molding is suppressed.
すなわち、本発明は、以下の態様を有する。
［１］ ＥＶＯＨ樹脂、及びチタン化合物を含有するＥＶＯＨ樹脂組成物であって、
前記チタン化合物の金属換算含有量が、ＥＶＯＨ樹脂組成物の質量あたり０．００１ｐｐｍ以上５ｐｐｍ未満であるＥＶＯＨ樹脂組成物。
［２］ ［１］記載のＥＶＯＨ樹脂組成物からなるペレット。
［３］ ［１］記載のＥＶＯＨ樹脂組成物からなる層を少なくとも１層備える多層構造体。
［４］ ［１］記載のＥＶＯＨ樹脂組成物を製造する方法であって、
前記ＥＶＯＨ樹脂とチタン化合物とを含有する組成物原料を溶融混合する工程を備える、ＥＶＯＨ樹脂組成物の製造方法。
［５］ ［３］記載の多層構造体を製造する方法であって、
前記ＥＶＯＨ樹脂組成物からなる層を溶融成形する工程を備える、多層構造体の製造方法。
That is, the present invention has the following aspects.
[1] An EVOH resin composition containing an EVOH resin and a titanium compound,
An EVOH resin composition in which the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 5 ppm per mass of the EVOH resin composition.
[2] A pellet made of the EVOH resin composition described in [1].
[3] A multilayer structure comprising at least one layer made of the EVOH resin composition according to [1].
[4] A method for producing the EVOH resin composition according to [1], comprising:
A method for producing an EVOH resin composition, comprising a step of melt-mixing composition raw materials containing the EVOH resin and a titanium compound.
[5] A method for manufacturing the multilayer structure according to [3], comprising:
A method for producing a multilayer structure, comprising the step of melt-molding a layer made of the EVOH resin composition.
本発明のＥＶＯＨ樹脂組成物は、溶融成形時におけるＥＶＯＨ樹脂の着色変化を抑制することができ、ロングラン性に優れる。 The EVOH resin composition of the present invention can suppress color change of EVOH resin during melt molding, and has excellent long-run properties.
以下、本発明の実施形態例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施形態に限定されない。
なお、本発明において「Ｘ～Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」又は「好ましくはＹより小さい」の意も包含する。
また、「Ｘ以上」（Ｘは任意の数字）又は「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」又は「Ｙ未満であることが好ましい」旨の意図も包含する。
Hereinafter, the present invention will be described in more detail based on embodiments of the present invention, but the present invention is not limited to these embodiments.
In addition, in the present invention, when expressed as "X to Y" (X, Y are arbitrary numbers), unless otherwise specified, it means "more than or equal to X and less than or equal to Y", and also means "preferably greater than X" or "preferably It also includes the meaning of "less than Y".
In addition, when expressed as "more than or equal to X" (X is any number) or "less than or equal to Y" (Y is any number), it is also possible to indicate that "it is preferably greater than X" or "it is preferably less than Y". It also includes intent.
＜ＥＶＯＨ樹脂組成物＞
本発明の一実施態様に係るＥＶＯＨ樹脂組成物（以下、「本ＥＶＯＨ樹脂組成物」と称する）は、ＥＶＯＨ樹脂を主成分とし、特定微量のチタン化合物を含有するものである。 すなわち、本ＥＶＯＨ樹脂組成物は、ベース樹脂がＥＶＯＨ樹脂であり、本ＥＶＯＨ樹脂組成物におけるＥＶＯＨ樹脂の含有量は、通常７０質量％以上、好ましくは８０質量％以上、より好ましくは９０質量％以上、特に好ましくは９５質量％以上である。
以下、各成分について説明する。
<EVOH resin composition>
An EVOH resin composition according to one embodiment of the present invention (hereinafter referred to as "this EVOH resin composition") has an EVOH resin as a main component and contains a specific trace amount of a titanium compound. That is, in the present EVOH resin composition, the base resin is an EVOH resin, and the content of EVOH resin in the present EVOH resin composition is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. , particularly preferably 95% by mass or more.
Each component will be explained below.
〔ＥＶＯＨ樹脂〕
本発明で用いるＥＶＯＨ樹脂は、通常、エチレンとビニルエステル系モノマーとの共重合体であるエチレン－ビニルエステル系共重合体をケン化させることにより得られる樹脂であり、非水溶性の熱可塑性樹脂である。
[EVOH resin]
The EVOH resin used in the present invention is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin. It is.
前記ビニルエステル系モノマーとしては、市場入手性や製造時の不純物処理効率がよい点から、代表的には酢酸ビニルが用いられる。酢酸ビニル以外の他のビニルエステル系モノマーとしては、例えばギ酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、バーサチック酸ビニル等の脂肪族ビニルエステル、安息香酸ビニル等の芳香族ビニルエステル等があげられるが、通常炭素数３～２０、好ましくは炭素数４～１０、特に好ましくは炭素数４～７の脂肪族ビニルエステルが用いられる。これらは通常単独で用いるが、必要に応じて複数種を同時に用いてもよい。 As the vinyl ester monomer, vinyl acetate is typically used because of its market availability and good efficiency in treating impurities during production. Examples of vinyl ester monomers other than vinyl acetate include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and versatic acid. Examples include aliphatic vinyl esters such as vinyl, aromatic vinyl esters such as vinyl benzoate, and aliphatic vinyls having usually 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. Esters are used. These are usually used alone, but multiple types may be used simultaneously if necessary.
前記エチレンとビニルエステル系モノマーとを共重合させる重合法としては、公知の任意の重合法、例えば溶液重合、懸濁重合、エマルジョン重合等を用いて行うことができるが、一般的にはメタノールを溶媒とする溶液重合が用いられる。また、得られたエチレン－ビニルエステル系共重合体のケン化も公知の方法で行い得る。
このようにして製造されるＥＶＯＨ樹脂は、エチレン由来の構造単位とビニルアルコール構造単位を主とし、ケン化されずに残存する若干量のビニルエステル構造単位を含むものである。
The copolymerization method for copolymerizing ethylene and the vinyl ester monomer can be carried out using any known polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization, etc., but generally methanol is used. Solution polymerization using a solvent is used. Furthermore, the obtained ethylene-vinyl ester copolymer may be saponified by a known method.
The EVOH resin produced in this manner is mainly composed of structural units derived from ethylene and vinyl alcohol structural units, and contains a small amount of vinyl ester structural units that remain without being saponified.
前記ＥＶＯＨ樹脂におけるエチレン構造単位の含有量は、通常２０～６０モル％、好ましくは２５～５０モル％、特に好ましくは２５～３５モル％である。前記エチレン構造単位の含有量は、ビニルエステル系モノマーとエチレンとを共重合させる際のエチレンの圧力によって制御することができ、かかる含有量が低すぎる場合は、高湿下のガスバリア性、溶融成形性が低下する傾向があり、逆に高すぎる場合は、ガスバリア性が低下する傾向がある。
なお、かかるエチレン構造単位の含有量は、ＩＳＯ１４６６３に基づいて測定することができる。
The content of ethylene structural units in the EVOH resin is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 35 mol%. The content of the ethylene structural unit can be controlled by the pressure of ethylene when copolymerizing the vinyl ester monomer and ethylene, and if this content is too low, the gas barrier property under high humidity, melt molding On the other hand, if it is too high, gas barrier properties tend to decrease.
Note that the content of such ethylene structural units can be measured based on ISO14663.
前記ＥＶＯＨ樹脂におけるケン化度は、通常９０～１００モル％、好ましくは９５～１００モル％、特に好ましくは９９～１００モル％である。前記ケン化度は、エチレン－ビニルエステル系共重合体をケン化する際のケン化触媒（通常、水酸化ナトリウム等のアルカリ性触媒が用いられる）の量、温度、時間等によって制御でき、かかるケン化度が低すぎる場合にはガスバリア性、熱安定性、耐湿性等が低下する傾向がある。
かかるＥＶＯＨ樹脂のケン化度は、ＪＩＳ Ｋ６７２６（ただし、ＥＶＯＨ樹脂は水／メタノール溶媒に均一に溶解した溶液として用いる）に基づいて測定することができる。
The saponification degree of the EVOH resin is usually 90 to 100 mol%, preferably 95 to 100 mol%, particularly preferably 99 to 100 mol%. The degree of saponification can be controlled by the amount, temperature, time, etc. of the saponification catalyst (usually an alkaline catalyst such as sodium hydroxide is used) when saponifying the ethylene-vinyl ester copolymer. If the degree of oxidation is too low, gas barrier properties, thermal stability, moisture resistance, etc. tend to deteriorate.
The degree of saponification of such EVOH resin can be measured based on JIS K6726 (however, the EVOH resin is used as a solution uniformly dissolved in a water/methanol solvent).
前記ＥＶＯＨ樹脂におけるメルトフローレート（ＭＦＲ）（２１０℃、荷重２１６０ｇ）は、通常０．５～１００ｇ／１０分であり、好ましくは１～５０ｇ／１０分、特に好ましくは３～３５ｇ／１０分である。かかるＭＦＲが大きすぎる場合には、製膜時の安定性が損なわれる傾向があり、小さすぎる場合には粘度が高くなり過ぎて溶融押出しが困難となる傾向がある。
前記ＭＦＲは、ＥＶＯＨ樹脂の重合度の指標となるものであり、エチレンとビニルエステル系モノマーを共重合する際の重合開始剤の量や、溶媒の量によって調整することができる。
The melt flow rate (MFR) (210° C., load 2160 g) of the EVOH resin is usually 0.5 to 100 g/10 minutes, preferably 1 to 50 g/10 minutes, particularly preferably 3 to 35 g/10 minutes. be. If the MFR is too large, stability during film formation tends to be impaired, and if it is too small, the viscosity tends to become too high, making melt extrusion difficult.
The MFR is an index of the degree of polymerization of the EVOH resin, and can be adjusted by adjusting the amount of polymerization initiator and the amount of solvent when copolymerizing ethylene and vinyl ester monomer.
また、前記ＥＶＯＨ樹脂には、本発明の効果を阻害しない範囲で、以下に示すコモノマーに由来する構造単位が、さらに含まれていてもよい（例えばＥＶＯＨ樹脂の１０モル％以下）。
前記コモノマーとしては、例えばプロピレン、１－ブテン、イソブテン等のオレフィン類、３－ブテン－１－オール、３－ブテン－１，２－ジオール、４－ペンテン－１－オール、５－ヘキセン－１，２－ジオール等のヒドロキシ基含有α－オレフィン類やそのエステル化物、アシル化物等の誘導体；２－メチレンプロパン－１，３－ジオール、３－メチレンペンタン－１，５－ジオール等のヒドロキシアルキルビニリデン類；１，３－ジアセトキシ－２－メチレンプロパン、１，３－ジプロピオニルオキシ－２－メチレンプロパン、１，３－ジブチリルオキシ－２－メチレンプロパン等のヒドロキシアルキルビニリデンジアセテート類；アクリル酸、メタクリル酸、クロトン酸、（無水）フタル酸、（無水）マレイン酸、（無水）イタコン酸等の不飽和酸類あるいはその塩あるいはアルキル基の炭素数が１～１８のモノ又はジアルキルエステル類；アクリルアミド、アルキル基の炭素数が１～１８のＮ－アルキルアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、２－アクリルアミドプロパンスルホン酸あるいはその塩、アクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその４級塩等のアクリルアミド類；メタアクリルアミド、アルキル基の炭素数が１～１８のＮ－アルキルメタクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミド、２－メタクリルアミドプロパンスルホン酸あるいはその塩、メタクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその４級塩等のメタクリルアミド類；Ｎ－ビニルピロリドン、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド等のＮ－ビニルアミド類；アクリルニトリル、メタクリルニトリル等のシアン化ビニル類；アルキル基の炭素数が１～１８のアルキルビニルエーテル、ヒドロキシアルキルビニルエーテル、アルコキシアルキルビニルエーテル等のビニルエーテル類；塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、臭化ビニル等のハロゲン化ビニル化合物類；トリメトキシビニルシラン等のビニルシラン類；酢酸アリル、塩化アリル等のハロゲン化アリル化合物類；アリルアルコール、ジメトキシアリルアルコール等のアリルアルコール類；トリメチル－（３－アクリルアミド－３－ジメチルプロピル）－アンモニウムクロリド、アクリルアミド－２－メチルプロパンスルホン酸等のコモノマーがあげられる。これらは単独でもしくは２種以上併せて用いることができる。
Further, the EVOH resin may further contain a structural unit derived from a comonomer shown below (eg, 10 mol% or less of the EVOH resin) within a range that does not impede the effects of the present invention.
Examples of the comonomer include olefins such as propylene, 1-butene, and isobutene, 3-buten-1-ol, 3-buten-1,2-diol, 4-penten-1-ol, 5-hexene-1, Hydroxy group-containing α-olefins such as 2-diol, and derivatives thereof such as esters and acylated products; Hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol ; Hydroxyalkyl vinylidene diacetates such as 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyryloxy-2-methylenepropane; Acrylic acid, methacrylic Acid, unsaturated acids such as crotonic acid, phthalic acid (anhydride), maleic acid (anhydride), and itaconic acid (anhydride), or their salts, or mono- or dialkyl esters with an alkyl group having 1 to 18 carbon atoms; acrylamide, alkyl Acrylamides such as N-alkylacrylamide, N,N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salt, acrylamidepropyldimethylamine, its acid salt, or its quaternary salt; meth Acrylamide, N-alkylmethacrylamide whose alkyl group has 1 to 18 carbon atoms, N,N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or its salt, methacrylamidepropyldimethylamine or its acid salt, or its quaternary Methacrylamides such as salts; N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide; vinylcyanides such as acrylonitrile and methacrylnitrile; Vinyl ethers such as alkyl vinyl ether, hydroxyalkyl vinyl ether, and alkoxyalkyl vinyl ether; Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and vinyl bromide; Vinyl silanes such as trimethoxyvinylsilane; Allyl acetate , allyl halides such as allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; comonomers such as trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride and acrylamide-2-methylpropanesulfonic acid. can be given. These can be used alone or in combination of two or more.
なかでも、ヒドロキシ基含有α－オレフィン類が好ましく、特には３－ブテン－１，２－ジオール、５－ヘキセン－１，２－ジオールが好ましい。前記ヒドロキシ基含有α－オレフィン類を共重合した場合、得られるＥＶＯＨ樹脂は、側鎖に１級水酸基を有することとなる。このような側鎖に１級水酸基を有するＥＶＯＨ樹脂、特には側鎖に１，２－ジオール構造を有するＥＶＯＨ樹脂は、ガスバリア性を保持しつつ二次成形性が良好になる点で好ましい。 Among these, hydroxy group-containing α-olefins are preferred, with 3-butene-1,2-diol and 5-hexene-1,2-diol being particularly preferred. When the hydroxy group-containing α-olefins are copolymerized, the resulting EVOH resin will have a primary hydroxyl group in the side chain. Such an EVOH resin having a primary hydroxyl group in the side chain, particularly an EVOH resin having a 1,2-diol structure in the side chain, is preferable because it maintains gas barrier properties and has good secondary moldability.
前記ＥＶＯＨ樹脂が、側鎖に１級水酸基を有する場合、当該１級水酸基を有するモノマー由来の構造単位の含有量は、ＥＶＯＨ樹脂の通常０．１～２０モル％、好ましくは０．５～１５モル％、特に好ましくは１～１０モル％である。 When the EVOH resin has a primary hydroxyl group in the side chain, the content of the structural unit derived from the monomer having the primary hydroxyl group is usually 0.1 to 20 mol%, preferably 0.5 to 15% by mole of the EVOH resin. mol %, particularly preferably 1 to 10 mol %.
また、前記ＥＶＯＨ樹脂としては、エステル化、ウレタン化、アセタール化、シアノエチル化、オキシアルキレン化等の「後変性」されたＥＶＯＨ樹脂を用いることもできる。 Further, as the EVOH resin, it is also possible to use an EVOH resin that has been "post-modified" such as esterification, urethanization, acetalization, cyanoethylation, or oxyalkylenation.
前記後変性されたＥＶＯＨ樹脂を用いる場合、その変性率は、通常１０モル％以下であり、好ましくは４モル％以下である。ＥＶＯＨ樹脂の変性率が高すぎる場合、熱劣化しやすくなり、ロングラン性が低下する傾向がある。 When using the post-modified EVOH resin, the modification rate is usually 10 mol% or less, preferably 4 mol% or less. If the modification rate of the EVOH resin is too high, it tends to be easily thermally degraded and its long run properties tend to decrease.
さらに、前記ＥＶＯＨ樹脂は、エチレン構造単位の含有量、ケン化度、重合度、共重合成分等が異なるＥＶＯＨ樹脂の混合物であってもよい。 Further, the EVOH resin may be a mixture of EVOH resins having different contents of ethylene structural units, degrees of saponification, degrees of polymerization, copolymerization components, and the like.
〔チタン化合物〕
前記チタン化合物としては、例えば無機チタン化合物、有機チタン化合物があげられる。なお、チタン化合物は単独でもしくは２種以上を併せて用いてもよい。なかでも無機チタン化合物が好ましい。
[Titanium compound]
Examples of the titanium compound include inorganic titanium compounds and organic titanium compounds. Note that the titanium compounds may be used alone or in combination of two or more. Among them, inorganic titanium compounds are preferred.
前記無機チタン化合物としては、例えばチタン酸化物、チタン水酸化物、チタン塩化物、チタンの無機塩等があげられる。
前記チタン酸化物としては、例えば酸化チタン（II）、酸化チタン（III）、酸化チタン（IV）、亜酸化チタン等があげられる。
前記チタン水酸化物としては、例えば水酸化第一チタン、水酸化第二チタン等があげられる。
前記チタン塩化物としては、例えば塩化第一チタン、塩化第二チタン等があげられる。 前記チタンの無機塩としては、例えばリン酸チタン、硫酸チタン等があげられる。
なかでも、チタン酸化物が好ましく、酸化チタン（IV）がより好ましく、ルチル型の酸化チタン（IV）が特に好ましい。
Examples of the inorganic titanium compound include titanium oxide, titanium hydroxide, titanium chloride, and inorganic salts of titanium.
Examples of the titanium oxide include titanium (II) oxide, titanium (III) oxide, titanium (IV) oxide, and titanium suboxide.
Examples of the titanium hydroxide include titanous titanium hydroxide, titanium dihydroxide, and the like.
Examples of the titanium chloride include titanous titanium chloride and titanium chloride. Examples of the inorganic salt of titanium include titanium phosphate and titanium sulfate.
Among these, titanium oxide is preferred, titanium (IV) oxide is more preferred, and rutile type titanium (IV) oxide is particularly preferred.
前記有機チタン化合物としては、例えば酢酸チタン、酪酸チタン、ステアリン酸チタン等のカルボン酸チタン等があげられる。 Examples of the organic titanium compound include titanium carboxylates such as titanium acetate, titanium butyrate, and titanium stearate.
なお、前記チタン化合物は、ＥＶＯＨ樹脂組成物中でチタン化合物として、存在する場合の他、イオン化した状態、あるいはＥＶＯＨ樹脂や他の配位子と相互作用した錯体の状態で存在していてもよい。 In addition, the titanium compound may exist in the EVOH resin composition as a titanium compound, or may exist in an ionized state or in a complex state that interacts with the EVOH resin or other ligands. .
前記チタン化合物の平均粒径は、通常０．００１～１００μｍであり、好ましくは０．０１～５０μｍであり、より好ましくは０．０１５～２０μｍである。チタン化合物の平均粒径が前記範囲内であると、着色抑制効果に優れる傾向がある。 The average particle size of the titanium compound is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.015 to 20 μm. When the average particle size of the titanium compound is within the above range, the effect of suppressing coloring tends to be excellent.
前記チタン化合物の金属換算含有量は、ＥＶＯＨ樹脂組成物の質量あたり０．００１ｐｐｍ以上５ｐｐｍ未満である。好ましくは０．０１～３ｐｐｍであり、より好ましくは０．０３～１ｐｐｍであり、特に好ましくは０．０５～０．５ｐｐｍである。チタン化合物の含有量を前記範囲とすることで、溶融成形時の熱劣化による着色変化を抑制することができ、ロングラン性に優れる。また、チタン化合物の含有量が少なすぎると、着色変化を抑制する効果が低下し、含有量が多すぎるとＥＶＯＨ樹脂の熱分解が起こりやすくなり着色しやすくなる。 The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 5 ppm per mass of the EVOH resin composition. It is preferably 0.01 to 3 ppm, more preferably 0.03 to 1 ppm, particularly preferably 0.05 to 0.5 ppm. By setting the content of the titanium compound within the above range, color change due to thermal deterioration during melt molding can be suppressed, resulting in excellent long-run properties. Moreover, if the content of the titanium compound is too small, the effect of suppressing color change will be reduced, and if the content is too large, thermal decomposition of the EVOH resin will easily occur and coloration will occur.
前記チタン化合物の金属換算含有量は、本ＥＶＯＨ樹脂組成物を白金るつぼに秤取り、バーナーおよび電気炉で順次灰化し、かかる灰化物を硝酸およびふっ化水素酸で加熱分解し、希硝酸と希ふっ化水素酸の混酸で処理して定容して得られた定容液中のチタンをＩＣＰ質量分析装置（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、Ａｇｉｌｅｎｔ ８８００）を用い、ＩＣＰ質量分析法で測定することにより定量することができる。 The metal equivalent content of the titanium compound is determined by weighing the present EVOH resin composition in a platinum crucible, incinerating it sequentially with a burner and electric furnace, heating the ashed product with nitric acid and hydrofluoric acid, and decomposing it with dilute nitric acid and diluted diluted nitric acid. Titanium in a fixed volume solution obtained by treatment with a mixed acid of hydrofluoric acid was determined by ICP mass spectrometry using an ICP mass spectrometer (manufactured by Agilent Technologies, Agilent 8800). can do.
一般的にＥＶＯＨ樹脂は、熱劣化によって着色が発生する。これは、熱によりＥＶＯＨ樹脂が劣化してラジカルが発生し、このラジカルによりＥＶＯＨ樹脂の水酸基が脱水され、ＥＶＯＨ樹脂の主鎖に二重結合が生成し、かかる部位が反応起点となり、さらに脱水が促進され、ＥＶＯＨ樹脂の主鎖に共役ポリエン構造が形成されるためと考えられる。
これに対し、本ＥＶＯＨ樹脂組成物は、特定微量のチタン化合物を含有することにより、ＥＶＯＨ樹脂の熱劣化による着色変化が抑制され、ロングラン性に優れるものである。 通常、ＥＶＯＨ樹脂組成物にチタン化合物を含有させた場合、チタンイオンにより、ＥＶＯＨ樹脂組成物が着色すると考えられるため、当業者であればチタン化合物の使用を避けることが技術常識である。しかしながら、本発明では、このような技術常識に反して、特定微量のチタン化合物物を用いる場合に、熱劣化による着色変化が抑制されたＥＶＯＨ樹脂組成物が得られることを見出したのである。
すなわち、チタンは、４価のイオンとして安定であり、微量であっても前記のようなＥＶＯＨ樹脂の主鎖の二重結合に配位し、キレートを形成する等によって安定化し、ポリエン構造の形成を抑制しているものと推測される。
Generally, EVOH resin becomes discolored due to thermal deterioration. This is because the EVOH resin deteriorates due to heat and radicals are generated, and these radicals dehydrate the hydroxyl group of the EVOH resin, forming a double bond in the main chain of the EVOH resin, and this site becomes the reaction starting point, causing further dehydration. This is thought to be due to the formation of a conjugated polyene structure in the main chain of the EVOH resin.
On the other hand, the present EVOH resin composition contains a specific trace amount of a titanium compound, thereby suppressing color change due to thermal deterioration of the EVOH resin and exhibiting excellent long-run properties. Normally, when a titanium compound is contained in an EVOH resin composition, it is thought that the EVOH resin composition is colored by titanium ions, so it is common general knowledge for those skilled in the art to avoid the use of titanium compounds. However, in the present invention, contrary to such common technical knowledge, it has been found that when a specific trace amount of a titanium compound is used, an EVOH resin composition in which color change due to thermal deterioration is suppressed can be obtained.
In other words, titanium is stable as a tetravalent ion, and even if it is in a small amount, it coordinates with the double bond in the main chain of the EVOH resin as described above, stabilizes it by forming a chelate, etc., and forms a polyene structure. It is assumed that this suppresses the
［その他の熱可塑性樹脂］
本ＥＶＯＨ樹脂組成物には、ＥＶＯＨ樹脂以外の熱可塑性樹脂を、本発明の効果を阻害しない範囲（例えば本ＥＶＯＨ樹脂組成物の通常３０質量％以下、好ましくは２０質量％以下、特に好ましくは１０質量％以下）にて含有することができる。
他の熱可塑性樹脂としては、公知の熱可塑性樹脂を用いることができ、例えば、ポリエステル系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル系樹脂、ポリカーボネート系樹脂、アイオノマー、ポリ塩化ビニリデン、ポリエステルエラストマー、ポリウレタンエラストマー、塩素化ポリエチレン、塩素化ポリプロピレン等があげられる。これらは単独でもしくは２種以上併せて用いることができる。
[Other thermoplastic resins]
The present EVOH resin composition contains a thermoplastic resin other than the EVOH resin within a range that does not impede the effects of the present invention (for example, usually 30% by mass or less, preferably 20% by mass or less, particularly preferably 10% by mass or less of the present EVOH resin composition). mass% or less).
As other thermoplastic resins, known thermoplastic resins can be used, such as polyester resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, ionomers, polyvinylidene chloride, polyester elastomers, and polyurethane elastomers. , chlorinated polyethylene, chlorinated polypropylene, etc. These can be used alone or in combination of two or more.
［その他の配合剤］
また、本ＥＶＯＨ樹脂組成物には、本発明の効果を阻害しない範囲において、一般にＥＶＯＨ樹脂に配合する配合剤が含有されていてもよい。上記配合剤としては、例えば、無機複塩（例えばハイドロタルサイト等）、可塑剤（例えばエチレングリコール、グリセリン、ヘキサンジオール等の脂肪族多価アルコール等）、酸素吸収剤［例えばアルミニウム粉、亜硫酸カリウム等の無機系酸素吸収剤；アスコルビン酸、さらにその脂肪酸エステルや金属塩等、没食子酸、水酸基含有フェノールアルデヒド樹脂等の多価フェノール類、テルペン化合物、三級水素含有樹脂と遷移金属とのブレンド物（例えば、ポリプロピレンとコバルトの組合せ）、炭素－炭素不飽和結合含有樹脂と遷移金属とのブレンド物（例えばポリブタジエンとコバルトの組合せ）、光酸化崩壊性樹脂（例えばポリケトン）、アントラキノン重合体（例えばポリビニルアントラキノン）等や、さらにこれらの配合物に光開始剤（ベンゾフェノン等）や、上記以外の酸化防止剤や消臭剤（活性炭等）を添加したもの等の高分子系酸素吸収剤］、熱安定剤、光安定剤、紫外線吸収剤、着色剤、帯電防止剤、界面活性剤（ただし、滑剤として用いるものを除く）、抗菌剤、アンチブロッキング剤、充填材（例えば無機フィラー等）等を配合してもよい。これらの化合物は、単独でもしくは２種以上併せて用いることができる。
[Other combination agents]
Further, the present EVOH resin composition may contain additives that are generally blended into EVOH resins within a range that does not impede the effects of the present invention. Examples of the above compounding agents include inorganic double salts (e.g. hydrotalcite, etc.), plasticizers (e.g. aliphatic polyhydric alcohols such as ethylene glycol, glycerin, hexanediol, etc.), oxygen absorbers [e.g. aluminum powder, potassium sulfite, etc. Inorganic oxygen absorbers such as ascorbic acid, its fatty acid esters and metal salts, gallic acid, polyhydric phenols such as hydroxyl group-containing phenol aldehyde resin, terpene compounds, blends of tertiary hydrogen-containing resins and transition metals. (e.g., a combination of polypropylene and cobalt), blends of carbon-carbon unsaturated bond-containing resins and transition metals (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and polymeric oxygen absorbers such as those containing photoinitiators (benzophenone, etc.), antioxidants and deodorants (activated carbon, etc.) other than those listed above], thermally stable Contains additives, light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, anti-blocking agents, fillers (e.g. inorganic fillers, etc.). It's okay. These compounds can be used alone or in combination of two or more.
［ＥＶＯＨ樹脂組成物の製造方法］
本ＥＶＯＨ樹脂組成物は、例えば、前記ＥＶＯＨ樹脂、チタン化合物を、公知の方法、例えばドライブレンド法、溶融混合法、溶液混合法、含浸法等によって混合することにより製造でき、これらのなかでも、前記ＥＶＯＨ樹脂とチタン化合物とを含有する組成物原料を溶融混合する工程を備えることにより製造することが好ましい。また、これらの製造方法は、任意に組み合わせることも可能である。
[Method for manufacturing EVOH resin composition]
The present EVOH resin composition can be produced, for example, by mixing the EVOH resin and the titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, It is preferable to manufacture by including a step of melt-mixing composition raw materials containing the EVOH resin and a titanium compound. Moreover, these manufacturing methods can also be combined arbitrarily.
前記ドライブレンド法としては、例えば（ｉ）ペレット状のＥＶＯＨ樹脂と、チタン化合物を、タンブラー等を用いてドライブレンドする方法等があげられる。 Examples of the dry blending method include (i) a method in which pelletized EVOH resin and a titanium compound are dry blended using a tumbler or the like.
前記溶融混合法としては、例えば（ii）ペレット状のＥＶＯＨ樹脂と、チタン化合物とをドライブレンドしたドライブレンド物を溶融混練する方法や、（iii）溶融状態のＥＶＯＨ樹脂にチタン化合物を添加して溶融混練する方法等があげられる。 Examples of the melt mixing method include (ii) a method of melt-kneading a dry blend obtained by dry blending pellet-shaped EVOH resin and a titanium compound, and (iii) a method of adding a titanium compound to a molten EVOH resin. Examples include a method of melting and kneading.
前記溶液混合法としては、例えば（iv）市販のＥＶＯＨ樹脂を用いて溶液を調製し、ここにチタン化合物を配合し、凝固成形し、その後、公知の手段により固液分離して乾燥する方法や、（ｖ）ＥＶＯＨ樹脂の製造過程で、ケン化前のエチレン－ビニルエステル系共重合体溶液やＥＶＯＨ樹脂の均一溶液（水／アルコール溶液等）にチタン化合物を含有させた後、凝固成形し、その後、公知の手段により固液分離して乾燥する方法等があげられる。 Examples of the solution mixing method include (iv) a method in which a solution is prepared using commercially available EVOH resin, a titanium compound is blended therein, solidified and molded, and then solid-liquid separation is performed by known means and dried; , (v) In the manufacturing process of EVOH resin, a titanium compound is contained in an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution (water/alcohol solution, etc.) of EVOH resin, and then solidified and molded, Thereafter, methods include solid-liquid separation and drying using known means.
前記含浸法としては、例えば（vi）ペレット状のＥＶＯＨ樹脂を、チタン化合物を含有する水溶液と接触させ、ＥＶＯＨ樹脂中にチタン化合物を含有させた後、乾燥する方法等があげられる。
前記チタン化合物を含有する水溶液としては、チタン化合物の水溶液や、チタン化合物を、各種薬剤を含む水に浸漬することでチタンイオンを溶出させたものを用いることができる。
なお、前記含浸法において、チタン化合物の含有量（金属換算）は、ＥＶＯＨ樹脂を浸漬する水溶液中のチタン化合物の濃度や浸漬温度、浸漬時間等によって制御することが可能である。
前記浸漬温度、浸漬時間としては、通常、０．５～４８時間、好ましくは１～３６時間であり、浸漬温度は通常１０～４０℃、好ましくは２０～３５℃である。
Examples of the impregnation method include (vi) a method in which pelletized EVOH resin is brought into contact with an aqueous solution containing a titanium compound, the titanium compound is incorporated into the EVOH resin, and then dried.
As the aqueous solution containing the titanium compound, an aqueous solution of a titanium compound or a titanium compound obtained by immersing the titanium compound in water containing various chemicals to elute titanium ions can be used.
In the impregnation method, the content of the titanium compound (metal equivalent) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, and the like.
The immersion temperature and time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.
前記各製造方法における乾燥方法としては、種々の乾燥方法を採用することが可能であり、静置乾燥、流動乾燥のいずれでもよい。また、これらを組み合わせて行うこともできる。 As the drying method in each of the above manufacturing methods, various drying methods can be employed, and either stationary drying or fluidized drying may be used. Moreover, these can also be performed in combination.
前述のとおり、本発明においては、上記の異なる方法を組み合わせることが可能である。なかでも、生産性や本発明の効果がより顕著な樹脂組成物が得られる点で、溶融混合法が好ましく、特には（ii）の方法が好ましい。また、前記その他の熱可塑性樹脂、その他の配合剤を用いる場合も、前記の製造方法に従い、常法により配合すればよい。 As mentioned above, in the present invention, it is possible to combine the different methods described above. Among these, the melt-mixing method is preferred, and the method (ii) is particularly preferred, since a resin composition with more remarkable productivity and the effects of the present invention can be obtained. Further, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.
このような前記各製造方法によって得られる本ＥＶＯＨ樹脂組成物の形状は任意であるが、ペレットであることが好ましい。
前記ペレットとしては、例えば、球形、オーバル形、円柱形、立方体形、直方体形等があるが、通常、オーバル形、又は円柱形であり、その大きさは、後に成形材料として用いる場合の利便性の観点から、オーバル形の場合は短径が通常１～１０ｍｍ、好ましくは２～６ｍｍであり、更に好ましくは２．５～５．５ｍｍであり、長径は通常１．５～３０ｍｍ、好ましくは３～２０ｍｍ、更に好ましくは３．５～１０ｍｍである。また、円柱形の場合は底面の直径が通常１～６ｍｍ、好ましくは２～５ｍｍであり、長さは通常１～６ｍｍ、好ましくは２～５ｍｍである。
また、前記各製造方法で用いるペレット状のＥＶＯＨ樹脂の形状、大きさも同様であることが好ましい。
Although the shape of the present EVOH resin composition obtained by each of the above-mentioned manufacturing methods is arbitrary, pellets are preferable.
The pellets include, for example, a spherical shape, an oval shape, a cylinder shape, a cubic shape, a rectangular parallelepiped shape, etc., but they are usually oval or cylindrical, and the size of the pellets depends on the convenience when later used as a molding material. From this point of view, in the case of an oval shape, the short axis is usually 1 to 10 mm, preferably 2 to 6 mm, more preferably 2.5 to 5.5 mm, and the long axis is usually 1.5 to 30 mm, preferably 3 mm. ~20mm, more preferably 3.5~10mm. Further, in the case of a cylindrical shape, the diameter of the bottom surface is usually 1 to 6 mm, preferably 2 to 5 mm, and the length is usually 1 to 6 mm, preferably 2 to 5 mm.
Further, it is preferable that the shape and size of the pellet-shaped EVOH resin used in each of the above manufacturing methods are also the same.
本ＥＶＯＨ樹脂組成物は、溶融成形時に加熱された場合であっても、着色変化が抑制され、ロングラン性に優れるものであり、加熱前のＹＩ値（イエローインデックス）に対する加熱後のＹＩ値の比（加熱後ＹＩ値／加熱前ＹＩ値）は、通常４．５以下であり好ましくは、４．２以下であり特に好ましくは３．９以下である。加熱前のＹＩ値に対する加熱後のＹＩ値の比が上記範囲であると、着色がより抑制できる傾向がある。ちなみに、加熱前のＹＩ値に対する加熱後のＹＩ値の比が４．８を超えると、熱劣化による着色が大きいと判断され、好ましくない。なお、前記加熱前のＹＩ値に対する加熱後のＹＩ値の比の下限は、通常１である。 This EVOH resin composition suppresses color change even when heated during melt molding and has excellent long-run properties, and the ratio of the YI value after heating to the YI value (yellow index) before heating. (YI value after heating/YI value before heating) is usually 4.5 or less, preferably 4.2 or less, and particularly preferably 3.9 or less. When the ratio of the YI value after heating to the YI value before heating is within the above range, coloring tends to be more suppressed. Incidentally, if the ratio of the YI value after heating to the YI value before heating exceeds 4.8, it is judged that coloring due to thermal deterioration is large, which is not preferable. Note that the lower limit of the ratio of the YI value after heating to the YI value before heating is usually 1.
前記加熱前のＹＩ値は、本ＥＶＯＨ樹脂組成物を１～５ｍｍ角に粉砕した粉砕物を、内径３２ｍｍ、高さ３０ｍｍの円筒に充填し、擦きった状態で、分光色差計ＳＥ６０００（日本電色工業社製）を用いて測定することにより得られる。
また、前記加熱後のＹＩ値は、前記１～５ｍｍ角に粉砕した本ＥＶＯＨ樹脂組成物を、空気雰囲気下のオーブン内で１５０℃、５時間加熱処理したものを、同様の方法で測定することにより得られる。
The YI value before heating is determined by filling a cylinder with an inner diameter of 32 mm and a height of 30 mm with the EVOH resin composition crushed into 1 to 5 mm squares, and measuring with a spectrocolorimeter SE6000 (Nippon Electric Power Co., Ltd.). (manufactured by Iroki Kogyo Co., Ltd.).
In addition, the YI value after heating is measured by the same method after heating the present EVOH resin composition crushed into 1 to 5 mm square pieces at 150°C for 5 hours in an oven under an air atmosphere. It is obtained by
本ＥＶＯＨ樹脂組成物の含水率は、通常、０．０１～０．５質量％であり、好ましくは０．０５～０．３５質量％、特に好ましくは０．１～０．３質量％である。 The moisture content of the EVOH resin composition is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, particularly preferably 0.1 to 0.3% by mass. .
なお、本ＥＶＯＨ樹脂組成物の含水率は以下の方法により測定・算出されるものである。
本ＥＶＯＨ樹脂組成物の乾燥前質量（Ｗ1）を電子天秤にて秤量し、１５０℃の熱風乾燥機中で５時間乾燥させ、デシケーター中で３０分間放冷後の質量（Ｗ2）を秤量し、下記式より算出する。
含水率（質量％）＝［（Ｗ1－Ｗ2）／Ｗ1］×１００
The water content of the EVOH resin composition is measured and calculated by the following method.
Weigh the mass (W 1 ) of the EVOH resin composition before drying using an electronic balance, dry it in a hot air dryer at 150°C for 5 hours, and weigh the mass (W 2 ) after leaving it to cool in a desiccator for 30 minutes. It is calculated using the formula below.
Moisture content (mass%) = [(W 1 - W 2 )/W 1 ] x 100
また、本ＥＶＯＨ樹脂組成物の形状がペレットである場合、溶融成形時のフィード性を安定させる点で、ペレットの表面に公知の滑剤を付着させることも好ましい。滑剤の種類としては、例えば、炭素数１２以上の高級脂肪酸（例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、オレイン酸等）、高級脂肪酸エステル（高級脂肪酸のメチルエステル、イソプロピルエステル、ブチルエステル、オクチルエステル等）、高級脂肪酸アミド（例えば、ラウリン酸アミド、ミリスチン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド等の飽和高級脂肪酸アミド；オレイン酸アミド、エルカ酸アミド等の不飽和高級脂肪酸アミド、エチレンビスステアリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、エチレンビスラウリン酸アミド等のビス高級脂肪酸アミド等）、低分子量ポリオレフィン（例えば分子量５００～１００００程度の低分子量ポリエチレン、又は低分子量ポリプロピレン等、又はその酸変性品）、炭素数６以上の高級アルコール、エステルオリゴマー、フッ化エチレン樹脂等があげられる。これらの化合物は、単独でもしくは２種以上併せて用いることができる。また、かかる滑剤の含有量は、本ＥＶＯＨ樹脂組成物の通常５質量％以下、好ましくは１質量％以下である。なお、下限は通常０質量％である。 Further, when the present EVOH resin composition is in the form of pellets, it is also preferable to attach a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Types of lubricants include, for example, higher fatty acids having 12 or more carbon atoms (for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (higher fatty acid methyl esters, isopropyl esters, butyl ester, octyl ester, etc.), higher fatty acid amides (for example, saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.); Saturated higher fatty acid amide, ethylene bis stearamide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, bis higher fatty acid amide such as ethylene bis lauric acid amide, etc.), low molecular weight polyolefin (for example, low molecular weight of about 500 to 10,000) Examples include polyethylene, low molecular weight polypropylene, etc., or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, fluorinated ethylene resins, and the like. These compounds can be used alone or in combination of two or more. Further, the content of such a lubricant is usually 5% by mass or less, preferably 1% by mass or less of the EVOH resin composition. Note that the lower limit is usually 0% by mass.
このようにして得られた本ＥＶＯＨ樹脂組成物は、ペレット、あるいは粉末状や液体状といった、さまざまな形態に調製され、各種の成形物の成形材料として提供される。特に本発明においては、溶融成形用の材料として提供される場合、本発明の効果がより効率的に得られる傾向があり好ましい。
なお、本ＥＶＯＨ樹脂組成物には、本ＥＶＯＨ樹脂組成物に用いられるＥＶＯＨ樹脂以外の樹脂を混合して得られる樹脂組成物も含まれる。
The EVOH resin composition thus obtained is prepared in various forms such as pellets, powder, and liquid, and provided as a molding material for various molded products. In particular, in the present invention, it is preferable to provide the material as a material for melt molding, since the effects of the present invention tend to be more efficiently obtained.
Note that the present EVOH resin composition also includes a resin composition obtained by mixing resins other than the EVOH resin used in the present EVOH resin composition.
前記成形物としては、例えば本ＥＶＯＨ樹脂組成物から成形された単層フィルムをはじめとして、本ＥＶＯＨ樹脂組成物からなる層を有する多層構造体等があげられる。 Examples of the molded product include a single layer film molded from the present EVOH resin composition, and a multilayer structure having layers made of the present EVOH resin composition.
［多層構造体］
本発明の一実施形態に係る多層構造体（以下、「本多層構造体」と称する）は、本ＥＶＯＨ樹脂組成物からなる層を備えるものである。本ＥＶＯＨ樹脂組成物からなる層（以下、単に「本ＥＶＯＨ樹脂組成物層」という）は、本ＥＶＯＨ樹脂組成物以外の熱可塑性樹脂を主成分とする他の基材（以下、基材に用いられる樹脂を「基材樹脂」と略記することがある）と積層することで、さらに強度を付与したり、本ＥＶＯＨ樹脂組成物層を水分等の影響から保護したり、他の機能を付与することができる。
[Multilayer structure]
A multilayer structure according to an embodiment of the present invention (hereinafter referred to as "this multilayer structure") includes a layer made of the present EVOH resin composition. A layer made of the present EVOH resin composition (hereinafter simply referred to as "the present EVOH resin composition layer") may be formed by using another base material (hereinafter referred to as a base material) containing a thermoplastic resin as a main component other than the present EVOH resin composition. (sometimes abbreviated as "base material resin"), the EVOH resin composition layer can be further strengthened, protected from the effects of moisture, etc., and provided with other functions. be able to.
前記基材樹脂としては、例えば直鎖状低密度ポリエチレン、低密度ポリエチレン、超低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、エチレン－プロピレン（ブロックおよびランダム）共重合体、エチレン－α－オレフィン（炭素数４～２０のα－オレフィン）共重合体等のポリエチレン系樹脂、ポリプロピレン、プロピレン－α－オレフィン（炭素数４～２０のα－オレフィン）共重合体等のポリプロピレン系樹脂、ポリブテン、ポリペンテン、ポリ環状オレフィン系樹脂（環状オレフィン構造を主鎖および側鎖の少なくとも一方を有する重合体）等の（未変性）ポリオレフィン系樹脂や、これらのポリオレフィン類を不飽和カルボン酸又はそのエステルでグラフト変性した不飽和カルボン酸変性ポリオレフィン系樹脂等の変性オレフィン系樹脂を含む広義のポリオレフィン系樹脂、アイオノマー、エチレン－酢酸ビニル共重合体、エチレン－アクリル酸共重合体、エチレン－アクリル酸エステル共重合体、ポリエステル系樹脂、ポリアミド系樹脂（共重合ポリアミドも含む）、ポリ塩化ビニル、ポリ塩化ビニリデン、アクリル系樹脂、ポリスチレン系樹脂、ビニルエステル系樹脂、ポリエステル系エラストマー、ポリウレタン系エラストマー、ポリスチレン系エラストマー、塩素化ポリエチレン、塩素化ポリプロピレン等のハロゲン化ポリオレフィン、芳香族又は脂肪族ポリケトン類等があげられる。これらは、単独でもしくは２種以上併せて用いることができる。 Examples of the base resin include linear low density polyethylene, low density polyethylene, very low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene (block and random) copolymers, ethylene-α-olefin ( Polyethylene resins such as copolymers (α-olefins having 4 to 20 carbon atoms), polypropylene, polypropylene resins such as propylene-α-olefin (α-olefins having 4 to 20 carbon atoms) copolymers, polybutene, polypentene, (Unmodified) polyolefin resins such as polycyclic olefin resins (polymers with a cyclic olefin structure having at least one of a main chain and a side chain), and graft-modified polyolefins of these polyolefins with unsaturated carboxylic acids or their esters. Broadly defined polyolefin resins including modified olefin resins such as unsaturated carboxylic acid modified polyolefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyesters resin, polyamide resin (including copolyamide polyamide), polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, polystyrene elastomer, chlorinated polyethylene , halogenated polyolefins such as chlorinated polypropylene, aromatic or aliphatic polyketones, and the like. These can be used alone or in combination of two or more.
これらのうち、疎水性樹脂である、ポリアミド系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリスチレン系樹脂が好ましく、より好ましくは、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリ環状オレフィン系樹脂およびこれらの不飽和カルボン酸変性ポリオレフィン系樹脂等のポリオレフィン系樹脂である。 Among these, hydrophobic resins such as polyamide resins, polyolefin resins, polyester resins, and polystyrene resins are preferred, and polyethylene resins, polypropylene resins, polycyclic olefin resins, and unsaturated resins thereof are more preferred. These are polyolefin resins such as carboxylic acid-modified polyolefin resins.
本多層構造体の層構成は、本ＥＶＯＨ樹脂組成物層をａ（ａ１、ａ２、・・・）、基材樹脂層をｂ（ｂ１、ｂ２、・・・）とするとき、ａ／ｂ、ｂ／ａ／ｂ、ａ／ｂ／ａ、ａ１／ａ２／ｂ、ａ／ｂ１／ｂ２、ｂ２／ｂ１／ａ／ｂ１／ｂ２、ｂ２／ｂ１／ａ／ｂ１／ａ／ｂ１／ｂ２等、任意の組み合わせが可能である。また、本多層構造体を製造する過程で発生する端部や不良品等を再溶融成形して得られる、本ＥＶＯＨ樹脂組成物と本ＥＶＯＨ樹脂組成物以外の熱可塑性樹脂との混合物を含むリサイクル層をＲとするとき、ｂ／Ｒ／ａ、ｂ／Ｒ／ａ／ｂ、ｂ／Ｒ／ａ／Ｒ／ｂ、ｂ／ａ／Ｒ／ａ／ｂ、ｂ／Ｒ／ａ／Ｒ／ａ／Ｒ／ｂ等とすることも可能である。本多層構造体の層の数はのべ数にて通常２～１５、好ましくは３～１０である。上記の層構成において、それぞれの層間には、必要に応じて接着性樹脂を含有する接着性樹脂層を介在させてもよい。 The layer structure of the present multilayer structure is a/b, where the present EVOH resin composition layer is a (a1, a2, ...) and the base resin layer is b (b1, b2, ...). b/a/b, a/b/a, a1/a2/b, a/b1/b2, b2/b1/a/b1/b2, b2/b1/a/b1/a/b1/b2, etc., arbitrary A combination of these is possible. In addition, recycling includes a mixture of the present EVOH resin composition and a thermoplastic resin other than the present EVOH resin composition, which is obtained by remelting and molding the edges and defective products generated in the process of manufacturing the present multilayer structure. When the layer is R, b/R/a, b/R/a/b, b/R/a/R/b, b/a/R/a/b, b/R/a/R/a /R/b etc. is also possible. The total number of layers in the present multilayer structure is usually 2 to 15, preferably 3 to 10. In the above layered structure, an adhesive resin layer containing an adhesive resin may be interposed between each layer, if necessary.
前記接着性樹脂としては、公知のものを使用でき、基材樹脂層「ｂ」に用いる熱可塑性樹脂の種類に応じて適宜選択すればよい。代表的には不飽和カルボン酸又はその無水物をポリオレフィン系樹脂に付加反応やグラフト反応等により化学的に結合させて得られるカルボキシ基を含有する変性ポリオレフィン系重合体をあげることができる。上記カルボキシ基を含有する変性ポリオレフィン系重合体としては、例えば、無水マレイン酸グラフト変性ポリエチレン、無水マレイン酸グラフト変性ポリプロピレン、無水マレイン酸グラフト変性エチレン－プロピレン（ブロックおよびランダム）共重合体、無水マレイン酸グラフト変性エチレン－エチルアクリレート共重合体、無水マレイン酸グラフト変性エチレン－酢酸ビニル共重合体、無水マレイン酸変性ポリ環状オレフィン系樹脂、無水マレイン酸グラフト変性ポリオレフィン系樹脂等があげられる。これらは単独でもしくは２種以上を併せて用いてもよい。 As the adhesive resin, any known adhesive resin can be used, and may be appropriately selected depending on the type of thermoplastic resin used for the base resin layer "b". A typical example is a modified polyolefin polymer containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin by an addition reaction, a graft reaction, or the like. Examples of the modified polyolefin polymer containing a carboxyl group include maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymers, and maleic anhydride graft-modified polypropylene (block and random) copolymers. Examples include graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft-modified ethylene-vinyl acetate copolymer, maleic anhydride-modified polycyclic olefin resin, maleic anhydride graft-modified polyolefin resin, and the like. These may be used alone or in combination of two or more.
本多層構造体において、本ＥＶＯＨ樹脂組成物層と基材樹脂層との間に、接着性樹脂層を用いる場合、接着性樹脂層が本ＥＶＯＨ樹脂組成物層の両側に位置することから、疎水性に優れた接着性樹脂を用いることが好ましい。 In this multilayer structure, when an adhesive resin layer is used between the present EVOH resin composition layer and the base resin layer, since the adhesive resin layer is located on both sides of the present EVOH resin composition layer, the hydrophobic It is preferable to use an adhesive resin with excellent properties.
上記基材樹脂、接着性樹脂には、本発明の趣旨を阻害しない範囲（例えば樹脂全体に対して、３０質量％以下、好ましくは１０質量％以下）において、従来知られているような可塑剤、フィラー、クレー（モンモリロナイト等）、着色剤、酸化防止剤、帯電防止剤、滑剤、核材、ブロッキング防止剤、ワックス等を含んでいてもよい。これらは単独でもしくは２種以上併せて用いることができる。 The above-mentioned base resin and adhesive resin may contain conventionally known plasticizers within a range that does not impede the purpose of the present invention (for example, 30% by mass or less, preferably 10% by mass or less based on the entire resin). , fillers, clays (such as montmorillonite), colorants, antioxidants, antistatic agents, lubricants, core materials, antiblocking agents, waxes, and the like. These can be used alone or in combination of two or more.
前記本ＥＶＯＨ樹脂組成物層と上記基材樹脂層との積層（接着性樹脂層を介在させる場合を含む）は、公知の方法にて行うことができる。例えば、本ＥＶＯＨ樹脂組成物のフィルム、シート等に基材樹脂を溶融押出ラミネートする方法、基材樹脂層に本ＥＶＯＨ樹脂組成物を溶融押出ラミネートする方法、本ＥＶＯＨ樹脂組成物と基材樹脂とを共押出する方法、本ＥＶＯＨ樹脂組成物（層）と基材樹脂（層）とを有機チタン化合物、イソシアネート化合物、ポリエステル系化合物、ポリウレタン化合物等の公知の接着剤を用いてドライラミネートする方法、基材樹脂上に本ＥＶＯＨ樹脂組成物の溶液を塗工してから溶媒を除去する方法等があげられる。これらのなかでも、コストや環境の観点から考慮して、本ＥＶＯＨ樹脂組成物層を溶融成形する工程を備えることにより製造することが好ましく、具体的には共押出する方法が好ましい。 Lamination of the present EVOH resin composition layer and the base resin layer (including the case where an adhesive resin layer is interposed) can be performed by a known method. For example, a method of melt extrusion laminating a base resin on a film, sheet, etc. of the present EVOH resin composition, a method of melt extrusion laminating the present EVOH resin composition on a base resin layer, a method of melt extrusion laminating the present EVOH resin composition and a base resin, A method of dry laminating the present EVOH resin composition (layer) and a base resin (layer) using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound. Examples include a method in which a solution of the present EVOH resin composition is applied onto the base resin and then the solvent is removed. Among these, in view of cost and environment, it is preferable to manufacture the present EVOH resin composition layer by including a step of melt-molding it, and specifically, a coextrusion method is preferable.
本多層構造体は、必要に応じて（加熱）延伸処理を施してもよい。延伸処理は、一軸延伸、二軸延伸のいずれであってもよく、二軸延伸の場合は同時延伸であっても逐次延伸であってもよい。また、延伸方法としてはロール延伸法、テンター延伸法、チューブラー延伸法、延伸ブロー法、真空圧空成形等のうち延伸倍率の高いものも採用できる。延伸温度は、多層構造体の融点近傍の温度で、通常４０～１７０℃、好ましくは６０～１６０℃程度の範囲から選ばれる。延伸温度が低すぎる場合は延伸性が不良となり、高すぎる場合は安定した延伸状態を維持することが困難となる。 This multilayer structure may be subjected to (heating) stretching treatment if necessary. The stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, simultaneous stretching or sequential stretching may be performed. Further, as the stretching method, a method with a high stretching ratio among roll stretching methods, tenter stretching methods, tubular stretching methods, stretch blowing methods, vacuum-pressure forming, etc. can be adopted. The stretching temperature is selected from the range of usually 40 to 170°C, preferably about 60 to 160°C, near the melting point of the multilayer structure. If the stretching temperature is too low, the stretchability will be poor, and if it is too high, it will be difficult to maintain a stable stretched state.
また、延伸処理後の本多層構造体は、寸法安定性を付与することを目的として、熱固定を行ってもよい。熱固定は周知の手段で実施可能であり、例えば前記延伸処理された本多層構造体を、緊張状態を保ちながら通常８０～１８０℃、好ましくは１００～１６５℃で通常２～６００秒間程度熱処理を行う。 Further, the present multilayer structure after the stretching treatment may be heat-set for the purpose of imparting dimensional stability. Heat fixation can be carried out by well-known means. For example, the stretched multilayer structure is heat-treated at a temperature of usually 80 to 180°C, preferably 100 to 165°C, for about 2 to 600 seconds while maintaining a tensioned state. conduct.
前記延伸処理された本多層構造体をシュリンク用フィルムとして用いる場合には、熱収縮性を付与するために、上記の熱固定を行わず、例えば延伸処理後の本多層構造体に冷風を当てて冷却固定する等の処理を行えばよい。 When the stretched multilayer structure is used as a shrink film, in order to impart heat shrinkability, the above heat setting is not performed, and for example, cold air is applied to the stretched multilayer structure. Processing such as cooling and fixing may be performed.
本多層構造体（延伸したものを含む）の厚み、更には多層構造体を構成する本ＥＶＯＨ樹脂組成物層、基材樹脂層および接着性樹脂層の厚みは、層構成、基材樹脂の種類、接着性樹脂の種類、用途や包装形態、要求される物性等により一概にいえないが、本多層構造体（延伸したものを含む）の厚みは、通常１０～５０００μｍ、好ましくは３０～３０００μｍ、特に好ましくは５０～２０００μｍである。本ＥＶＯＨ樹脂組成物層は通常１～５００μｍ、好ましくは３～３００μｍ、特に好ましくは５～２００μｍであり、基材樹脂層は通常５～３０００μｍ、好ましくは１０～２０００μｍ、特に好ましくは２０～１０００μｍであり、接着性樹脂層は、通常０．５～２５０μｍ、好ましくは１～１５０μｍ、特に好ましくは３～１００μｍである。 The thickness of the present multilayer structure (including the stretched one) and the thickness of the present EVOH resin composition layer, base resin layer, and adhesive resin layer that constitute the multilayer structure are determined by the layer structure and the type of base resin. The thickness of the present multilayer structure (including the stretched one) is usually 10 to 5000 μm, preferably 30 to 3000 μm, although it cannot be definitively stated depending on the type of adhesive resin, application, packaging form, required physical properties, etc. Particularly preferred is 50 to 2000 μm. The EVOH resin composition layer is usually 1 to 500 μm, preferably 3 to 300 μm, particularly preferably 5 to 200 μm, and the base resin layer is usually 5 to 3000 μm, preferably 10 to 2000 μm, particularly preferably 20 to 1000 μm. The adhesive resin layer has a thickness of usually 0.5 to 250 μm, preferably 1 to 150 μm, particularly preferably 3 to 100 μm.
さらに、本多層構造体における本ＥＶＯＨ樹脂組成物層の基材樹脂層に対する厚みの比（本ＥＶＯＨ樹脂組成物層／基材樹脂層）は、各層が複数ある場合は最も厚みの厚い層同士の比にて、通常１／９９～５０／５０、好ましくは５／９５～４５／５５、特に好ましくは１０／９０～４０／６０である。また、本多層構造体における本ＥＶＯＨ樹脂組成物層の接着性樹脂層に対する厚み比（本ＥＶＯＨ樹脂組成物層／接着性樹脂層）は、各層が複数ある場合は最も厚みの厚い層同士の比にて、通常１０／９０～９９／１、好ましくは２０／８０～９５／５、特に好ましくは５０／５０～９０／１０である。 Furthermore, in the present multilayer structure, the thickness ratio of the present EVOH resin composition layer to the base resin layer (present EVOH resin composition layer/base material resin layer) is the thickness ratio between the thickest layers when there is a plurality of each layer. The ratio is usually 1/99 to 50/50, preferably 5/95 to 45/55, particularly preferably 10/90 to 40/60. In addition, the thickness ratio of the present EVOH resin composition layer to the adhesive resin layer in the present multilayer structure (present EVOH resin composition layer/adhesive resin layer) is the ratio of the thickest layers when there is a plurality of each layer. The ratio is usually 10/90 to 99/1, preferably 20/80 to 95/5, particularly preferably 50/50 to 90/10.
また、本多層構造体を用いてカップやトレイ状の多層容器を得ることも可能である。その場合は、通常絞り成形法が採用され、具体的には真空成形法、圧空成形法、真空圧空成形法、プラグアシスト式真空圧空成形法等があげられる。更に多層パリソン（ブロー前の中空管状の予備成形物）からチューブやボトル状の多層容器（積層体構造）を得る場合はブロー成形法が採用される。具体的には、押出ブロー成形法（双頭式、金型移動式、パリソンシフト式、ロータリー式、アキュムレーター式、水平パリソン式等）、コールドパリソン式ブロー成形法、射出ブロー成形法、二軸延伸ブロー成形法（押出式コールドパリソン二軸延伸ブロー成形法、射出式コールドパリソン二軸延伸ブロー成形法、射出成形インライン式二軸延伸ブロー成形法等）等があげられる。得られる積層体は必要に応じ、熱処理、冷却処理、圧延処理、印刷処理、ドライラミネート処理、溶液又は溶融コート処理、製袋加工、深絞り加工、箱加工、チューブ加工、スプリット加工等を行うことができる。 Moreover, it is also possible to obtain a multilayer container in the form of a cup or a tray using the present multilayer structure. In that case, a draw forming method is usually employed, and specific examples thereof include a vacuum forming method, a pressure forming method, a vacuum pressure forming method, a plug-assisted vacuum pressure forming method, and the like. Furthermore, when obtaining a tube- or bottle-shaped multilayer container (laminate structure) from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specifically, extrusion blow molding methods (double-head type, moving mold type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison blow molding, injection blow molding, biaxial stretching Examples include blow molding methods (extrusion type cold parison biaxial stretch blow molding method, injection type cold parison biaxial stretch blow molding method, injection molding inline type biaxial stretch blow molding method, etc.). The obtained laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc. as necessary. Can be done.
本ＥＶＯＨ樹脂組成物から成形された単層フィルムや、本多層構造体からなる袋およびカップ、トレイ、チューブ、ボトル等からなる容器や蓋材は、一般的な食品の他、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、飲料、化粧品、医薬品等の各種の包装材料容器として有用である。 Single-layer films molded from this EVOH resin composition, bags made from this multilayer structure, and containers and lids such as cups, trays, tubes, and bottles can be used for general foods, as well as mayonnaise, dressings, etc. It is useful as a variety of packaging material containers for seasonings, fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, pharmaceuticals, etc.
以下、実施例により本発明を具体的に説明する。但し、本発明は、以下の実施例により何ら限定されるものではない。
なお、例中「部」とあるのは、断りのない限り質量基準を意味する。
Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited in any way by the following examples.
In addition, "part" in the examples means a mass standard unless otherwise specified.
＜実施例１＞
ＥＶＯＨ樹脂として、エチレン構造単位の含有量２９モル％、ケン化度９９．６モル％、ＭＦＲ４ｇ／１０分（２１０℃、荷重２１６０ｇ）のＥＶＯＨ樹脂のペレットを用いた。
また、チタン化合物として、酸化チタン（富士フイルム和光純薬社製）を用いた。
前記ＥＶＯＨ樹脂ペレットに対し、前記酸化チタンを金属換算量としてＥＶＯＨ樹脂組成物の質量あたり０．１ｐｐｍとなるようにドライブレンドし、混合物を得た。
前記混合物を、二穴ダイを備えた二軸押出機（２０ｍｍφ）に供給し、下記の押出条件で押出、吐出されるストランドをベルトコンベア上にて空冷、固化させた。次に固化させたストランドを切断することでＥＶＯＨ樹脂組成物のペレットを得た。
［押出条件］
押出機設定温度（℃）：Ｃ１／Ｃ２／Ｃ３／Ｃ４／Ｃ５／Ｃ６
＝１５０／２００／２１０／２１０／２１０／２１０
<Example 1>
As the EVOH resin, pellets of EVOH resin having an ethylene structural unit content of 29 mol %, a degree of saponification of 99.6 mol %, and an MFR of 4 g/10 minutes (210° C., load 2160 g) were used.
Furthermore, titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as a titanium compound.
The EVOH resin pellets were dry-blended with the titanium oxide in a metal equivalent amount of 0.1 ppm per mass of the EVOH resin composition to obtain a mixture.
The mixture was supplied to a twin-screw extruder (20 mmφ) equipped with a two-hole die, extruded under the following extrusion conditions, and the discharged strand was air-cooled and solidified on a belt conveyor. Next, the solidified strands were cut to obtain pellets of the EVOH resin composition.
[Extrusion conditions]
Extruder setting temperature (℃): C1/C2/C3/C4/C5/C6
=150/200/210/210/210/210
＜実施例２＞
実施例１において、酸化チタンの配合量を金属換算量としてＥＶＯＨ樹脂組成物の質量あたり１ｐｐｍに変更した以外は、実施例１と同様にしてＥＶＯＨ樹脂組成物のペレットを得た。
<Example 2>
Pellets of an EVOH resin composition were obtained in the same manner as in Example 1, except that the amount of titanium oxide was changed to 1 ppm per mass of the EVOH resin composition in terms of metal.
＜比較例１＞
実施例１において、酸化チタンを用いなかった以外は、実施例１と同様にしてＥＶＯＨ樹脂組成物のペレットを得た。
<Comparative example 1>
Pellets of an EVOH resin composition were obtained in the same manner as in Example 1, except that titanium oxide was not used.
＜比較例２＞
実施例１において、酸化チタンの配合量を金属換算量としてＥＶＯＨ樹脂組成物の質量あたり１０ｐｐｍに変更した以外は、実施例１と同様にしてＥＶＯＨ樹脂組成物のペレットを得た。
<Comparative example 2>
Pellets of an EVOH resin composition were obtained in the same manner as in Example 1, except that the amount of titanium oxide was changed to 10 ppm per mass of the EVOH resin composition in metal terms.
得られた実施例１、２、および比較例１、２のＥＶＯＨ樹脂組成物のペレットを用いて、下記のロングラン性評価を行った。結果を後記の表１に示す。 Using the obtained pellets of the EVOH resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2, the following long-run performance evaluation was performed. The results are shown in Table 1 below.
〔ロングラン性評価〕
得られたＥＶＯＨ樹脂組成物のペレットを、粉砕機（ソメタニ産業社製、ＳＫＲ１６－２４０）にて６５０ｒｐｍで粉砕し、１～５ｍｍ角の粉砕物とした。
得られた粉砕物を、内径３２ｍｍ高さ３０ｍｍの円筒に粉砕物を充填し、擦きった状態で、分光色差計ＳＥ６０００（日本電色工業社製）にてＹＩ値を測定した。
また、前記粉砕物をオーブン内で１５０℃、５時間加熱処理したものについても同様にＹＩ値を測定した。
その後、加熱前のＹＩ値に対する加熱後のＹＩ値の比を算出した。
加熱前のＹＩ値に対する加熱後のＹＩ値の比が大きいほど、ＥＶＯＨ樹脂組成物が加熱後に黄色く着色変化していることを意味する。
[Long run performance evaluation]
The obtained pellets of the EVOH resin composition were crushed at 650 rpm using a crusher (manufactured by Sometani Sangyo Co., Ltd., SKR16-240) to obtain a crushed product of 1 to 5 mm square.
The obtained pulverized material was filled into a cylinder with an inner diameter of 32 mm and a height of 30 mm, and the YI value was measured using a spectrophotometer SE6000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in a rubbed state.
Further, the YI value was similarly measured for the pulverized product that had been heat-treated in an oven at 150° C. for 5 hours.
Thereafter, the ratio of the YI value after heating to the YI value before heating was calculated.
The larger the ratio of the YI value after heating to the YI value before heating, the more the EVOH resin composition is colored yellow after heating.
上記表１から、特定微量のチタン化合物を含有する実施例１、２のＥＶＯＨ樹脂組成物は、チタン化合物を含有しない比較例１のＥＶＯＨ樹脂組成物、チタン化合物を特定の範囲を超えて含有する比較例２のＥＶＯＨ樹脂組成物に比べてＹＩ値の比が小さく、加熱による着色変化が抑制されていることから、ロングラン性に優れるものであった。また、実施例１、２のＥＶＯＨ樹脂組成物からなる層を備える多層構造体も、着色変化が抑制されロングラン性に優れるという効果が得られる。 From Table 1 above, the EVOH resin compositions of Examples 1 and 2 that contain a specific trace amount of a titanium compound, the EVOH resin composition of Comparative Example 1 that does not contain a titanium compound, and the EVOH resin composition that contains a titanium compound beyond a specific range. Compared to the EVOH resin composition of Comparative Example 2, the YI value ratio was smaller and color change due to heating was suppressed, so it had excellent long-run properties. Further, the multilayer structure including the layers made of the EVOH resin compositions of Examples 1 and 2 also has the effect that color change is suppressed and excellent long-run properties are obtained.
本ＥＶＯＨ樹脂組成物は、溶融成形時の熱劣化による着色変化が抑制され、ロングラン性に優れることから、各種食品の他、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、飲料、化粧品、医薬品等の各種包装材料として有用である。 This EVOH resin composition suppresses color change due to heat deterioration during melt molding and has excellent long-run properties, so it can be used in various foods, seasonings such as mayonnaise and dressing, fermented foods such as miso, oils and fats such as salad oil, etc. It is useful as a variety of packaging materials for foods, beverages, cosmetics, pharmaceuticals, etc.
Claims (5)
前記チタン化合物の金属換算含有量が、エチレン－ビニルアルコール系共重合体組成物の質量あたり０．００１ｐｐｍ以上５ｐｐｍ未満であるエチレン－ビニルアルコール系共重合体組成物。 An ethylene-vinyl alcohol copolymer composition containing an ethylene-vinyl alcohol copolymer and a titanium compound,
An ethylene-vinyl alcohol copolymer composition, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 5 ppm per mass of the ethylene-vinyl alcohol copolymer composition.
前記エチレン－ビニルアルコール系共重合体とチタン化合物とを含有する組成物原料を溶融混合する工程を備える、エチレン－ビニルアルコール系共重合体組成物の製造方法。 A method for producing the ethylene-vinyl alcohol copolymer composition according to claim 1, comprising:
A method for producing an ethylene-vinyl alcohol copolymer composition, comprising the step of melt-mixing composition raw materials containing the ethylene-vinyl alcohol copolymer and a titanium compound.
前記エチレン－ビニルアルコール系共重合体組成物からなる層を溶融成形する工程を備える、多層構造体の製造方法。 A method for manufacturing the multilayer structure according to claim 3, comprising:
A method for producing a multilayer structure, comprising the step of melt-molding a layer made of the ethylene-vinyl alcohol copolymer composition.
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